Cargando…
Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
We have designed and synthesized a new tris-chelating polypyridine ligand (bpy(3)Ph) suitable to be used as a bridging ligand (BL) for constructing various supramolecular photocatalysts. This BL is a phenylene ring with three ethylene chains at 1, 3, and 5 positions, of which the other terminals are...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2019
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7069366/ https://www.ncbi.nlm.nih.gov/pubmed/32206277 http://dx.doi.org/10.1039/c9sc04532e |
_version_ | 1783505765747654656 |
---|---|
author | Cancelliere, Ambra M. Puntoriero, Fausto Serroni, Scolastica Campagna, Sebastiano Tamaki, Yusuke Saito, Daiki Ishitani, Osamu |
author_facet | Cancelliere, Ambra M. Puntoriero, Fausto Serroni, Scolastica Campagna, Sebastiano Tamaki, Yusuke Saito, Daiki Ishitani, Osamu |
author_sort | Cancelliere, Ambra M. |
collection | PubMed |
description | We have designed and synthesized a new tris-chelating polypyridine ligand (bpy(3)Ph) suitable to be used as a bridging ligand (BL) for constructing various supramolecular photocatalysts. This BL is a phenylene ring with three ethylene chains at 1, 3, and 5 positions, of which the other terminals are connected to 2,2′-bipyridine moieties. The ligand bpy(3)Ph has been used to prepare, according to a multi-step synthetic protocol, trinuclear supramolecular photocatalysts containing different metal subunits. In particular, the compounds Ru2Re and RuRe2 have been prepared, containing different ratios of components based on Ru(dmb)(3)(2+)-type and Re(dmb)(CO)(3)Cl-type units (dmb = 4,4′-dimethyl-2,2′-bipyridine), which can play the roles of photosensitizers and catalyst units for photocatalytic CO(2) reduction, respectively. The trinuclear model Ru3 and mononuclear and dinuclear Ru and Ru2 precursor metal complexes, containing free chelating sites, have also been synthesized using the same bridging ligand. The absorption spectra, redox behaviour and photophysical properties of the new species indicate that there is no strong electronic interaction among the Ru and Re units. The trinuclear complexes Ru2Re and RuRe2 could photocatalyze CO(2) reduction to CO with high selectivity (up to 97%), high efficiency (Φ(CO)s of 28% and 25%, respectively: BIH as a reductant), and high durability (TON(CO)s of 5232 and 6038, respectively: BIH as a reductant) which are the largest TONs for CO(2) reduction using supramolecular photocatalysts in homogeneous solutions. The absence of negligible accumulation of the mono-reduced form of the photosensitizer indicates fast electron transfer to the catalyst unit(s) through the relatively large bridging ligand and is proposed to contribute to the outstanding photocatalytic properties of the new species, including their durability. The relevant photocatalytic behaviour of the new systems indicates new avenues for the design of extended bridging ligands capable of efficiently and functionally integrating photosensitizers and catalysts towards the preparation of new, larger supramolecular photocatalysts for selective CO(2) reduction. |
format | Online Article Text |
id | pubmed-7069366 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-70693662020-03-23 Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring Cancelliere, Ambra M. Puntoriero, Fausto Serroni, Scolastica Campagna, Sebastiano Tamaki, Yusuke Saito, Daiki Ishitani, Osamu Chem Sci Chemistry We have designed and synthesized a new tris-chelating polypyridine ligand (bpy(3)Ph) suitable to be used as a bridging ligand (BL) for constructing various supramolecular photocatalysts. This BL is a phenylene ring with three ethylene chains at 1, 3, and 5 positions, of which the other terminals are connected to 2,2′-bipyridine moieties. The ligand bpy(3)Ph has been used to prepare, according to a multi-step synthetic protocol, trinuclear supramolecular photocatalysts containing different metal subunits. In particular, the compounds Ru2Re and RuRe2 have been prepared, containing different ratios of components based on Ru(dmb)(3)(2+)-type and Re(dmb)(CO)(3)Cl-type units (dmb = 4,4′-dimethyl-2,2′-bipyridine), which can play the roles of photosensitizers and catalyst units for photocatalytic CO(2) reduction, respectively. The trinuclear model Ru3 and mononuclear and dinuclear Ru and Ru2 precursor metal complexes, containing free chelating sites, have also been synthesized using the same bridging ligand. The absorption spectra, redox behaviour and photophysical properties of the new species indicate that there is no strong electronic interaction among the Ru and Re units. The trinuclear complexes Ru2Re and RuRe2 could photocatalyze CO(2) reduction to CO with high selectivity (up to 97%), high efficiency (Φ(CO)s of 28% and 25%, respectively: BIH as a reductant), and high durability (TON(CO)s of 5232 and 6038, respectively: BIH as a reductant) which are the largest TONs for CO(2) reduction using supramolecular photocatalysts in homogeneous solutions. The absence of negligible accumulation of the mono-reduced form of the photosensitizer indicates fast electron transfer to the catalyst unit(s) through the relatively large bridging ligand and is proposed to contribute to the outstanding photocatalytic properties of the new species, including their durability. The relevant photocatalytic behaviour of the new systems indicates new avenues for the design of extended bridging ligands capable of efficiently and functionally integrating photosensitizers and catalysts towards the preparation of new, larger supramolecular photocatalysts for selective CO(2) reduction. Royal Society of Chemistry 2019-12-14 /pmc/articles/PMC7069366/ /pubmed/32206277 http://dx.doi.org/10.1039/c9sc04532e Text en This journal is © The Royal Society of Chemistry 2020 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Cancelliere, Ambra M. Puntoriero, Fausto Serroni, Scolastica Campagna, Sebastiano Tamaki, Yusuke Saito, Daiki Ishitani, Osamu Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring |
title | Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
|
title_full | Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
|
title_fullStr | Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
|
title_full_unstemmed | Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
|
title_short | Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
|
title_sort | efficient trinuclear ru(ii)–re(i) supramolecular photocatalysts for co(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7069366/ https://www.ncbi.nlm.nih.gov/pubmed/32206277 http://dx.doi.org/10.1039/c9sc04532e |
work_keys_str_mv | AT cancelliereambram efficienttrinuclearruiireisupramolecularphotocatalystsforco2reductionbasedonanewtrischelatingbridgingligandbuiltaroundacentralaromaticring AT puntorierofausto efficienttrinuclearruiireisupramolecularphotocatalystsforco2reductionbasedonanewtrischelatingbridgingligandbuiltaroundacentralaromaticring AT serroniscolastica efficienttrinuclearruiireisupramolecularphotocatalystsforco2reductionbasedonanewtrischelatingbridgingligandbuiltaroundacentralaromaticring AT campagnasebastiano efficienttrinuclearruiireisupramolecularphotocatalystsforco2reductionbasedonanewtrischelatingbridgingligandbuiltaroundacentralaromaticring AT tamakiyusuke efficienttrinuclearruiireisupramolecularphotocatalystsforco2reductionbasedonanewtrischelatingbridgingligandbuiltaroundacentralaromaticring AT saitodaiki efficienttrinuclearruiireisupramolecularphotocatalystsforco2reductionbasedonanewtrischelatingbridgingligandbuiltaroundacentralaromaticring AT ishitaniosamu efficienttrinuclearruiireisupramolecularphotocatalystsforco2reductionbasedonanewtrischelatingbridgingligandbuiltaroundacentralaromaticring |